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Technical Report European Cement Research Academy European Cement Research Academy GmbH Tannenstrasse 2 40476 Duesseldorf, GERMANY Phone: +49-211-23 98 38-0 Fax: +49-211-23 98 38-500 [email protected] www.ecra-online.org Chairman of the advisory board: Daniel Gauthier Managing director: Martin Schneider Registration office: Duesseldorf Court of registration: Duesseldorf Commercial registration no.: 47580 Technical Report TR-ECRA 0049a/2013/M Guidance Document on BAT-BEP for Mercury in the Cement Industry Initial Outline No part of this report may be reproduced in any form, by photocopying, scanning, microfilm or otherwise, or incorporated into any information retrieval system without the written permission of the European Cement Research Academy. Neither the European Cement Research Academy nor the authors of this report shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential or other damages. Technical Report TR-ECRA 0049a/2013/M (31 May 2013) Page 2 of 24 Client: WBCSD – Cement Sustainability Initiative Ordering date: 23 April 2013 Client’s order number: – Our order number: 0120/2013/M Project manager: Robin Harrass Dr Ute Zunzer Person in charge: Dr Volker Hoenig Despatch date: 31 May 2013 Content: 24 pages Technical Report TR-ECRA 0049a/2013/M (31 May 2013) Page 3 of 24 Index of Contents 1 Regulatory Framework 4 1.1 Minamata Convention 4 1.2 European Union 4 1.3 USA 5 1.4 Other countries 6 2 Behaviour of mercury in cement process 7 2.1 Description of cement production process 7 2.2 Behaviour of mercury in cement production 8 2.2.1 Where does mercury come from? 9 2.2.2 Behaviour of mercury in the clinker burning process 10 2.2.3 Mercury releases from cement production 13 2.2.4 Known inventories 13 2.3 Safe enclosure of mercury 14 3 Mercury abatement techniques with regard to the European BAT Reference Document 15 3.1 Methods for removing mercury 15 3.1.1 Cement kiln dust shuttling 15 3.1.2 Enhanced trapping and removal using sorbents 16 3.1.2.1 Injection of activated carbon (ACI) or other sorbents 16 3.1.2.2 Use of oxidizing agents 17 3.1.3 Lignite coke filter (Polvitec) 17 3.1.4 Interactions with other gas cleaning technologies 18 3.1.4.1 Wet scrubbers 18 3.1.4.2 Selective catalytic reduction (SCR) 18 3.2 Emission monitoring 19 3.2.1 Monitoring of mercury emissions 19 3.2.2 Manual methods for mercury spot measurements 19 3.2.3 Continuous emission monitoring systems (CEMS) for long-term mercury measurements 20 3.2.4 Thermo-catalytic devices 21 3.2.5 High temperature cell 21 3.2.6 Wet-chemical devices 21 4 Best Available Technique and Best Environmental Practice 22 Annex: Bibliography 23 Technical Report TR-ECRA 0049a/2013/M (31 May 2013) Page 4 of 24 1 Regulatory Framework 1.1 Minamata Convention The Minamata Convention on Mercury as a global and legally binding treaty targets at the worldwide reduction of mercury emissions regulating their anthropogenic causes. It was initi- ated by the UNEP Governing Council in 2009. The import, export and production of mercury containing products such as batteries, switch- es, some medical devices and cosmetics will be banned by 2020. Plans to reduce and elimi- nate mercury emissions from artisanal and small-scale gold mining shall be established by countries, promoting mercury-free alternatives. Plans to minimize mercury emissions from existing industrial mercury emitters such as coal-fired power plants, cement factories or waste incinerating plants are to be drawn up while new facilities are to install the Best Avail- able Techniques. The Convention was agreed upon in January 2013 in Geneva, Switzerland at the Intergov- ernmental Negotiating Committee’s 5th session (INC5) and will be open to signature in Octo- ber 2013 in Minamata, Japan to come into force after being ratified by 50 countries. 1.2 European Union In the European Union, mercury emissions from cement plants co-incinerating waste fuels (alternative fuels) are regulated by the new Industrial Emissions Directive 2010/75/EU (IED) that brings together Directive 2008/1/EC (the ‘IPPC Directive’) and six other directives in a single directive on industrial emissions. It was to be transposed into the Member States’ leg- islations by 7 January 2013. No mercury limits have been fixed for cement plants using only regular fuels. The Directive is based on several principles1, namely a) An integrated approach meaning that permits must take into account the whole envi- ronmental performance of the plant, covering all aspects of the plants environmental im- pact to ensure a high level of protection of the environment taken as a whole. b) Best Available Techniques on which permit conditions and emission limits must be based on. The reference for setting permissions shall be documents containing infor- mation on the emission levels associated with the best available techniques (BAT con- clusions). These are relevant for plants not using waste fuels as well. c) Flexibility allowing the licensing authorities to set less strict emission limit values in spe- cific cases where the achievement of emission levels associated with BAT as described in the BAT conclusions would lead to disproportionately higher costs compared to the environmental benefits. d) Environmental inspections by authorities on a regular basis e) The public’s right to participate in the decision-making process, and to be informed of its consequences 1 see http://ec.europa.eu/environment/air/pollutants/stationary/ied/legislation.htm Technical Report TR-ECRA 0049a/2013/M (31 May 2013) Page 5 of 24 Installations for the production of cement clinker in rotary kilns with a production capacity ex- ceeding 500 tonnes per day or in other furnaces with a production capacity exceeding 50 tonnes per day, which are co-incinerating waste fuels, are subject to a mercury emission limit 3 of 0.05 mg/Nm at 10% O2 over a sampling period of 30 minutes to 8 hours. National legislative bodies may tighten this limit further, as it was by way of example imple- mented in Germany: Two mercury emission limit values are in place for cement plants co-incinerating waste.2 3 - A daily mean average limit of 0.03 mg/Nm at 10% O2 must be met. 3 - A half-hour mean average of 0.05 mg/Nm at 10% O2 specifically limits short-time peaks. 3 A higher daily limit of 0.05 mg/Nm at 10% O2 can be granted by the authorities if the opera- tor can show that the above mentioned limit value cannot be met due to mercury input from raw materials. Cement plants using only regular fuels are subject to a mercury emission limit 3 3 (daily rate) of 0.05 mg/Nm at 10% O2. 1.3 USA Since 2005, for cement kilns using hazardous waste as a fuel, a 12-hour rolling average limit for the mercury feed has to be established based on test run averages limiting the mercury content of the hazardous waste feed to 3.0 ppmw4 for existing kilns and 1.9 ppmw for new kilns. Additionally mercury emissions are limited either to 120 µg/dscm5 corrected to 7% oxy- gen, 12-hour rolling average when continuously monitored or to a hazardous waste feed maximum theoretical emission concentration (MTEC) of 120 µg/dscm. The standard for cement plants not burning hazardous wastes was revised to come into force in September 2010 for new sources and in September 2013 for existing sources intro- ducing new limits based on the amount of produced clinker, see Table 1. However in Febru- ary 2013 the compliance date for existing sources was postponed to September 2015 /FED 13/. Table 1 US-ELV for mercury emissions to be met by September 2015 /FED 11/ existing sources new sources (after 6 May 2009) 55 lb/MM t (US) of clinker 21 lb/MM t (US) of clinker 27.5 mg/t, 30-day rolling average, 10.5 mg/t, 30-day rolling average, equivalent to about 11 µg/Nm3 equivalent to about 4 µg/Nm3 Until the new standards come into force, cement plants with a commenced construction or reconstruction on or after 2 December 2005 must meet mercury emissions of 41 µg/dscm or alternatively use a packed bed or wet scrubber6 /FED 13/. 2 subject to 17. BImSchV 3 subject to TA Luft, currently under revision and expected to take over regulations established in 17. BImSchV 4 parts per million by weight 5 dry standard cubic meter 6 at 7% O2, based on a performance test or as ”maximum theoretical emission concentration“ based on the measured performance of the wet scrubber Technical Report TR-ECRA 0049a/2013/M (31 May 2013) Page 6 of 24 1.4 Other countries As shown in Table 2 not only ELVs themselves vary significantly from country to country and are to be distinguished by the use of waste derived fuels, but they also differ in influencing circumstances such as measurement technique or reference conditions. Table 2 National ELVs for mercury emissions for cement manufacturing in mg/Nm3, status: 2010 /based on REN 10/ Country without using waste using waste information Argentina no limit Australia 1.0 permit limit Bangladesh 0.20 Brazil 0.05 sum of Cd, Hg, and Tl: 0.2 or 0.28; at 7% O2 Chile 0.109 at 10% O2 Colombia 0.05 at 11% O2 Costa Rica 0.24 sum of Hg and Cd; at 10% O2 Ecuador under review; reference value: 0.05; at 10% O2 El Salvador 0.05 at 10% O2 India 0.2 Indonesia 5.0 0.2 at 7% O2 Korea 0.1 at 13% O2 Malaysia 10.0 at 12% CO2 Mexico 0.07 at 7% O2 Morocco 0.1 0.10 at 11% O2 Philippines 5.0 Thailand 0.10 at 7% O2 Venezuela 0.05 at 10% O2 Vietnam 0.5 for waste incinerators Technical Report TR-ECRA 0049a/2013/M (31 May 2013) Page 7 of 24 2 Behaviour of mercury in cement process 2.1 Description of cement production process Clinker production Limestone and clay or their natural mix, lime marl, which are the raw materials for cement clinker, are extracted from quarries typically close to the cement plant.
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